EP0114556A2

EP0114556A2 - Photographic recording material

Info

Publication number: EP0114556A2
Application number: EP83402475A
Authority: EP
Inventors: Kenneth Charles Mattes; Harold Chester Warren
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1982-12-20
Filing date: 1983-12-20
Publication date: 1984-08-01
Also published as: US4450222A; JPS59119349A; CA1182675A; EP0114556A3

Abstract

Image transfer photographic recording material is described which employs carbon black in an opaque layer or in an alkaline processing composition. The carbon black has a deactivating compound adsorbed thereto so that dye image-providing material can diffuse through the opaque layer, or processing composition, without any substantial adsorption thereof to the carbon black. The deactivating compound is incapable of releasing any dye moiety therefrom. Post-processing image dye diffusion is thereby lessened.

Description

This invention relates to a photographic recording material for color diffusion transfer photography and to an improvement whereby post-processing image dye diffusion is lessened.
Various formats for color, integral transfer photographic recording materials are described in the prior art. These formats include those where the image-receiving layer, which contains the photographic image for viewing, remains permanently attached and integral with the image generating and ancillary layers present in the structure when a transparent support is employed on the viewing side of the recording material. The image is formed by dyes, produced in the image generating units, diffusing through the layers of the structure to the dye image-receiving layer. After exposure an alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The emulsion layers are developed in proportion to the extent of the respective exposures, and the image dyes which are formed or released in the respective image generating layers begin to diffuse throughout the structure. At least a portion of the imagewise distribution of diffusible dyes diffuses to the dye image-receiving layer to form an image of the original subject.
All photographic systems require good image discrimination and low D_min values which do not change appreciably with time. However, in image transfer systems a problem sometimes occurs in that ^D _min, and sometimes D_max, continues to increase over a period of time. This is described in the art as "post-processing image dye density increase".
Carbon black is commonly employed in opaque layers of color diffusion transfer photographic recording materials to provide one or two sides of a chemical "darkroom" in which silver halide development and dye diffusion is initiated. Such opaque layers may be preformed in the photographic element. They may also be formed after processing of the element by means of an opaque processing composition which is inserted into the recording material. In either case, image dyes come into contact with or must pass through opaque layers containing carbon black.
The inherent adsorptive property of carbon presents a problem. When released dye migrating through an opaque carbon layer is adsorbed on the carbon surface, low D_max results. If this were an irreversible reaction, an increase in the amount of dye image-providing material might effectively recover theD . Unfortunately, however, dyes max adsorbed on the carbon are subsequently released either oxidatively or nonoxidatively, thus providing a post-processing image dye density increase.
Several apparently simple means for deactivating carbon might at first appear to be practical. For example, sulfur compounds are adsorbed strongly to the surface of carbon. However, the use of sulfur compounds is not practical in photographic systems since they might severely inhibit development or cause fog formation.
Also, forced oxidation of carbon black to modify the surface of the particles so that they absorb less color image dye and aggregate less has not been fully satisfactory since some color image dye is still absorbed by the carbon using this technique.
U.S. Patents 4,356,250, and 4,353,973 disclose the use of a cyan redox dye releasing (RDR) compound in the carbon layer. It is effective in providing a high initial D_max since it is adsorbed efficiently to the surface of the carbon. The cyan imaging dye that subsequently migrates through this carbon layer does not compete effectively for the adsorption sites. Although this provides a desirably high initial D_max, a secondary problem is created. Because the imaging material is an RDR compound, it will release cyan dye slowly under oxidative conditions and with keeping under some adverse conditions. This released dye diffuses to the mordant resulting in density increases that may be unacceptable in D_min areas.
The present invention provides a photographic recording material which comprises a support having thereon a dye image-receiving layer, an opaque carbon black layer and a silver halide emulsion layer which has in reactive association therewith a dye image-providing material wherein the recording material contains a dye image having post-processing stability.
The photographic recording material in accordance with this invention is characterized in that the carbon black has a deactivating compound adsorbed thereto which after processing is incapable of releasing any dye moiety therefrom.
The effect of the deactivating compound adsorbed to the carbon black is that released dye image-providing material can diffuse through the opaque layer without any substantial absorption thereof to the carbon black.
In a preferred embodiment of this invention, the deactivating compound has the following structural formula:
Ballast
in which formula:

a) Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic groups or polymeric groups) as to render the compound nondiffusible in the photographic recording material during development by an alkaline processing composition;
b) Z is
or is part of Y;
_c) G is OR¹ or NHR² where R¹ is hydrogen or a hydrolyzable moiety, including for example, acetyl, mono-, di-, or trichloroacetyl, perfluoroacyl, pyruvyl, alkoxyacyl, nitrobenzoyl, cyanobenzoyl, sulfonyl and sulfinyl; and R² is hydrogen or a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, sec-butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl,'octadecyl, dodecyl or sulfonamido, or a benzyl or phenethyl group (when R² is an alkyl group of greater than 6 carbon atoms, it can serve as a partial or sole Ballast group);
d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus or a 5- to 7-membered heterocyclic ring, such as pyrazolone or pyrimidine;
e) X is a moiety which is adsorbed to the carbon black and thus retards adsorption thereto of the dye image-providing material;
f) J is a bivalent linking group which is non- cleavable by oxidation; and
g) n is 1 or 2 and is 2 when G is OR¹ or when R² is hydrogen or an alkyl group of less than 8 carbon atoms.

In the above formula, X may be any moiety as long as part of the deactivating compound is adsorbed to the carbon black, thereby permitting the dye image-providing material to pass through the opaque layer without any substantial adsorption thereof to the carbon black. In a preferred embodiment, X may be a dye, a dye precursor or a moiety containing a series of canjugated π bonds.
J in the above formula can be any bivalent linking group, linking X to the rest of the compound, as long as it is not cleavable by oxidation. Such groups include, for example, -(CR^3R)_m -, -NR⁵-, -NR⁵-SO₂-, -NR⁵-PO₂-, -NR⁵-PO₃-, -NR³CO-, -NR³COR^5-,

-PO₂R⁵- or -P0_3R ^S-, where R³ and R⁴ each independently represents hydrogen, or a substituted or unsubstituted alkyl, aryl, aralkyl or alkaryl group; R⁵ is a substituted or unsubstituted alkyl, aryl, aralkyl or alkaryl group; and m is an integer of from 1 to 16. In a preferred embodiment J is -NHCO- or -0-.
Substituents which may be present on the R², _R ³, R⁴ or R⁵ alkyl, aryl, aralkyl or alkaryl groups described above include any substituent which has no adverse effect upon the ability of the deactivating compound to be adsorbed to the carbon black surfaces.
More preferred carbon adsorption deactivating compounds have the structural formula:
where Ballast, G, Y, J and n are defined as above, and Col is a dye, a dye precursor or a moiety containing a series of conjugated n bonds.
Dye moieties useful as X or Col are well known to those skilled in the art and include dyes such as azo, azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, merocyanine, nitro, quinoline, cyanine, indigoid, phthalocyanine and metal-complexed dyes. Dye precursors useful as X or Col include leuco dyes, oxichromic dyes and dyes which shift hypsochromically or bathochromically when subjected to a different environment such as a change in pH. Examples of such dye moieties are disclosed in U.S. Patent 3,928,312.
As noted above, X or Col can also be a moiety containing a series of conjugated n bonds. By this term is meant a series of alternating multiple and single bonds, such as unsaturated aliphatic chains or condensed aromatic rings, e.g., 1,3-butadiene, naphthalene, phenanthrene or pyrene.
G in the formula immediately above can also be OH, Y can be the atoms necessary to complete a naphthalene nucleus, Col is a dye, J is -NHCOR⁵- or -OR^5-, and R⁵ is a substituted or unsubstituted alkyl, aryl, aralkyl or alkaryl group and n is 2.
Specific compounds included within the scope of this invention include the following:
The carbon adsorption deactivating compounds described above are effective carbon adsorbers and produce good D_max/D_min image discrimination that is retained after incubation or long term keeping. The compounds can be conveniently incorporated in an opaque layer by dispersing them in an amide, phenol or ester coupler solvent.
The carbon adsorption deactivating compounds described above may be employed in an opaque layer in any concentration which is effective for the intended purpose. Good results are obtained at a concentration of from about 5 to about 25 mg/m² of element. If the carbon adsorption deactivating compound is employed in a processing composition, it can be employed in any amount which is effective for the intended purpose. Good results are obtained at concentrations of from about 0.5 to about 2.5 g/₁ of processing composition.
A photographic recording material in accordance with this invention may also comprise an alkaline processing composition comprising carbon black and means containing same for discharge within the recording material. The previously described opaque layer or the alkaline processing composition, or both, can contain a carbon adsorption deactivating compound as described above.
The described photographic recording material can also comprise a transparent cover sheet.
A process for lessening the amount of post-processing image dye diffusion from a color photographic transfer image comprises:

a) exposing a photographic recording material comprising a support having thereon a dye image-receiving layer, an opaque layer comprising carbon black and a carbon adsorption deactivating compound and at least one photosensitive silver halide emulsion layer having in reactive association therewith a dye image-providing material,
b) treating the recording material with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each o-f-the exposed silver halide emulsion layers, and
c) diffusing an imagewise distribution of dye image-providing material, which is formed as a function of development, through the opaque layer to a dye image-receiving layer to provide the transfer image, the carbon adsorption deactivating compound substantially preventing any dye image-providing material from being adsorbed on the surface of the carbon black, whereby, after processing has been completed, the amount of dye diffusing to the dye image-receiving layer is substantially eliminated.

A variety of silver halide developing agents can be used in this invention. Specific examples of developing agents or electron transfer agents (ETA's) include hydroquinone compounds, aminophenol compounds, catechol compounds, or phenylenediamine compounds. Highly preferred are ETA compounds such as 3-pyrazolidinone compounds. These ETA compounds are employed in the liquid processing composition or contained, at least in part, in a layer or layers of the photographic recording material to be activated by the alkaline processing composition, such as in the silver halide emulsion layers, the dye image-providing material layers, interlayers or image-receiving layer.
As noted above the alkaline processing composition can also contain carbon black and a deactivating compound adsorbed thereto as previously described.
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes materials that for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, in the described photographic recording materials in an alkaline medium, and preferably when processed in a medium having a pH of 11 or greater. The same meaning is to be attached to the term "immobile". The term "diffusible" has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the photographic recording materials in an alkaline medium. "Mobile" has the same meaning as "diffusible".
The term "in reactive association" is intended to mean that the materials can be in either the same or different layers, so long as the materials are accessible to one another.
The following examples are provided to further illustrate the invention.

Example 1 -- Carbon Absorption Deactivator In Opaque Layer (^D _max )

A) A control receiving element was prepared by coating the following layers in the order recited on a transparent poly(ethylene terephthalate) film support. Quantities are parenthetically given in grams per square meter.
- (1) image-receiving layer of poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride-co-divinylbenzene) (molar ratio 49/49/2) (2.3) and gelatin (2.3);
- (2) reflecting layer of titanium dioxide (16.0) and gelatin (2.6);
- (3) interlayer of gelatin (1.2) and bis(vinylsulfonyl)methyl ether (0.02);
- (4) opaque layer of carbon black (1.7), gelatin (1.2), oxidized developer scavenger 2-(2-octadecyl)-5-sulfohydroquinone potassium salt (0.02);
  and
- (5) overcoat layer of gelatin (10.8) and bis(vinylsulfonyl)methyl ether (0.12).
B) A comparison receiving element was prepared similar to A) except that a cyan RDR was employed in layer (4) as a carbon absorption deactivator at 22 mg/m` (as a 25 percent aqueous dispersion in N-n-butylactanilide with 1 percent Tamol® SN surfactant) (Tamol SN is a trademark of Rohm and Haas Company, U.S.A.). The cyan RDR employed was CYAN RDR A from Example 1 of U.S. Patent.4,353,973.
C-F) Receiving elements in accordance with this invention were prepared similar to A) except that compounds 1-4 above were employed in layer 4 at 22 _mg/_m ² (as a 25 percent aqueous dispersion in N-n-butylacetanilide with 1 percent Tamol® SN surfactant).

A cover sheet was prepared by coating the following layers, in the order recited, on a poly-(ethylene terephthalate) film support:

(1) an acid layer comprising poly(n-butyl acrylate- co-acrylic acid), (30:70 weight ratio equivalent to 140 meq. acid/m²); and
(2) a timing layer comprising 1.1 g/m² of a 1:1 physical mixture by weight of poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid latex) (weight ratio of 14/80/6) and a carboxy ester lactone formed by cyclization of a vinyl acetate-maleic anhydride copolymer in the presence of 1-butanol to produce a partial butyl ester, ratio of acid:ester of 15:85; and
(3) gelatin layer (3.8 g/m`) hardened at one percent with bis(vinylsulfonyl)methyl ether.

A dye-containing processing composition was prepared by dissolving 40 mg of the following cyan dye in 60 ml of 1 N potassium hydroxide. To this solution, 2.1 g/ℓ carboxymethylcellulose was added and the mixture was stirred for one hour. The structure of the cyan dye was:
A 2 ml aliquot of the dye in the processing composition was spread and laminated between the above receivers and the cover sheet using a pair of 75 µm gap undercut rollers. After a period of one week at room temperature, 20°C, 70 percent RH, the reflection density of the transferred dye on the receiver side was read at 650 nm, the x-max of the dye. The following results were obtained:
Under these conditions of "ideal transfer" involving no imaging chemistry, differences in density represent differences in the matrix through which the dye diffused. The dye migrating through the carbon-only opaque layer (control receiver A) gave the lowest density indicating adsorption of some of the dye on the carbon surface. The comparison carbon adsorption deactivator, cyan RDR A, and the carbon adsorption deactivators of the invention, Compounds 1-4, showed higher density on the receiver, indicating adsorption sites on the carbon were blocked to migrating dye. The density of dye transferred was essentially equivalent to that observed in a coating without any opacifying layer.
Although the comparison carbon adsorption deactivator cyan RDR A in the receiver gave a density equivalent to the compounds according to the invention, the comparison compound produced other problems as will be shown in the subsequent examples.

Example 2 -- Oxidative Release of Dye From Comparison Carbon Adsorption Deactivator (D_min)

Receiving elements according to Example 1 were prepared.
A light-sensitive element was prepared consisting of a 0.8 µm monodispersed silver bromoiodide emulsion (1.0 g Ag/m²) in 1.0 g/m² gelatin and hardened with 2 percent bis(vinylsulfonyl)methyl ether.
A processing composition was prepared containing:
An aliquot of the processing composition was spread and laminated between the receivers and a portion of the light-sensitive element using a pair of 75 µm gap undercut rollers. This and all subsequent operations were carried out in room light to insure fogging of the emulsion. After a period of 24 hours at room temperature, the reflection D_min density was read at 650 nm. The above procedure was repeated for a second test. The following results were obtained:
The control receiver A) with no carbon adsorption deactivator produced the lowest density. Although satisfactory from this standpoint, there is a problem in obtaining adequate dye transfer when no carbon deactivator is employed, as Example 1 has shown.
Receiver B) with the comparison carbon adsorption deactivating compound, Cyan RDR A, produced a very high D_min. This is due to the fogged silver halide being reduced to metallic silver, the 3-pyrazolidinone electron transfer agent being converted to its oxidized form, which in turn caused dye to be released from the Cyan RDR A.
In receivers C-F, no oxidative release occurred and a low D i was obtained. Since those receivers also produced a high D_max (Example 1), they gave the best image discrimination of the compounds tested.

Example 3 -- Incubation Tests

Receiving elements according to Example 1 were prepared using Compounds 1-6.
Cover sheets similar to those of Example 1 were prepared except that timing layer (2) coverage was 5.4 g/m².
A processing composition of 57 g carboxymethylcellulose and 47 g potassium hydroxide per liter of solution was prepared.
An aliquot of the processing composition was spread and laminated between the receiver and the cover sheet using a pair of 75 µm undercut rollers. After a period of 24 hours at 60°C, 70 percent RH, the reflection density was read at 650 nm. The above procedure was repeated for a second test. The following results were obtained.
The above results parallel the findings of Example 2. The receiver B) with the comparison carbon adsorption deactivating compound, cyan RDR A, produced a high stain, indicating dye release. The receivers C) to H) employing a carbon adsorption deactivating compound in accordance with this invention, however, had lower stain values than the comparison receiver.

Example 4 -- Lessening of Post-Process Dye Diffusion in a Multicolor Element

Cover sheets similar to those of Example 3 were prepared.

A) A control integral imaging-receiver element was prepared by coating the following layers in the order recited on a transparent poly(ethylene terephthalate) film support. Quantities are parenthetically given in grams per square meter, unless otherwise stated.
- (1) image-receiving layer of a poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzyl)ammonium sulfate-co-divinylbenzene) (molar ratio 49/49/2) (2.3) and gelatin (2.3);
- (2) reflecting layer of titanium dioxide (16.2) and gelatin (2.6);
- (3) opaque layer of carbon black (1.9), gelatin (1.2), and oxidized developer scavenger 2-(2-octadecyl)-5-sulfohydroquinone potassium salt (0.02);
- (4) cyan dye-providing layer of gelatin (0.44) and cyan RDR B (0.32) dispersed in N-n-butylacetanilide, RDR/solvent ratio 1:2;
- (5) interlayer of gelatin (0.54);
- (6) red-sensitive, direct-positive silver bromide emulsion (1.1 silver), gelatin (1.2), Nucleating Agent A (45 mg/Ag mole), 2-(2-octadecyl)-5-sul- fohydroquinone potassium salt (0.14), Nucleating Agent B (1.6 mg/Ag mole) and titanium dioxide (0.81);
- (7) interlayer of gelatin (1.2) and 2,5-di-sec-dodecylhydroquinone (1.2);
- (8) magenta dye-providing layer of magenta RDR C (0.43) dispersed in diethyllauramide, RDR/solvent ratio 1:2 and gelatin (0.65);
- (9) interlayer of gelatin (0.65);
- (10) green-sensitive, direct-positive silver bromide emulsion (0.92 silver), gelatin (0.76), Nucleating Agent A (11.0 mg/Ag mole), Nucleating Agent C (1.2 mg/Ag mole), 2-(2-octadecyl)-5-sulfo- hydroquinone potassium salt (0.034) and titanium dioxide (0.22);
- (11) interlayer of green-sensitive negative silver bromide emulsion (0.05 silver), gelatin (1.3) and 2,5-di-sec-dodecylhydroquinone (1.2);
- (12) yellow dye-providing layer of yellow RDR D (0.32) dispersed in di-n-butyl phthalate, RDR/solvent ratio 1:2, yellow RDR E (0.24) dispersed in di-n-butyl phthalate, RDR/solvent ratio 1:2, gelatin (1.2) and hardener bis(vinylsulfonyl)methane (.006);
- (13) blue-sensitive, direct-positive silver bromide emulsion (0.92 silver), gelatin (0.91), Nucleating Agent A (31 mg/Ag mole), Nucleating Agent C (1.1 mg/Ag mole), 2-(2-octadecyl)-5-sulfohydro- quinone potassium salt (0.034), t-butylhydroquinone monoacetate (0.016) and titanium dioxide (0.27); and
- (14) overcoat layer of gelatin (0.89) and 2,5-di-sec-dodecylhydroquinone (0.10).
The direct-positive emulsions are approximately 0.8p monodispersed, octahedral, internal image silver bromide emulsions, as described in U.S. Patent 3,923,513.
B) A comparison integral imaging-receiver element was prepared similar to A) except that opaque layer (3) contained CYAN RDR A (Example 1) (0.022) dispersed in N-n-butylacetanilide, RDR/solvent ratio of 1:2, as a carbon adsorption deactivator.
C) An integral imaging-receiver element according to the invention was prepared similar to B) except that Compound 8 was employed instead of CYAN RDR A.

The imaging-receiver elements were exposed in a sensitometer through a graduated density test object to yield a neutral at a Status A density of 1.0. The elements were then processed at 21°C by rupturing a pod containing the viscous processing composition described below between the imaging-receiver elements and the cover sheets described above, by using a pair of juxtaposed rollers to provide a processing gap of about 65pm. The processing composition was as follows:
water to 1 liter.
After a period of not less than one hour, the "fresh" sensitometry of the density curves were obtained by computer integration of the individual step Status A densities. The laminated unit was then incubated for two weeks at 32°C, 70% RH. The samples were read again and the change in red density from an original density of 1.0 was tabulated. The D_min change upon incubation was also determined. The following results were obtained:
The above results indicate that a much more stable sensitometry (less red density increase at a density of 1.0 and less D_min increase) was obtained using the carbon adsorption deactivator of the invention.

Claims

1. A photographic recording material comprising a support having thereon a dye image-receiving layer, an opaque layer comprising carbon black, and at least one silver halide emulsion layer having in reactive association therewith a dye image-providing material,
characterized in that said carbon black has a deactivating compound adsorbed thereto, said deactivating compound being incapable of releasing any dye moiety therefrom.

2. A photographic recording material according to claim 1 characterized in that said deactivating compound has the structural formula:

in which formula:

a) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photographic recording material during development by an alkaline processing composition;

b) Z is

or is part of Y;

c) G is _OR ¹ or NHR2 where R^l is hydrogen or a hydrolyzable moiety and R² is hydrogen or a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms;

d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus or a 5- to 7-membered heterocyclic ring;

e) X is a moiety which is adsorbed to said carbon black and thus retards adsorption thereto of said dye image-providing material;

f) J is a bivalent linking group which is non- cleavable by oxidation; and

g) n is 1 or 2 and is 2 when G is OR¹ or when _R ² is hydrogen or an alkyl group of less than 8 carbon atoms.

3. A photographic recording material according to claim 2 characterized in that X is a dye, a dye precursor or a moiety containing a series of conjugated π bonds.

4. A photographic recording material according to claim 2 characterized in that said deactivating compound has the structural formula:

where Ballast, G, Y, J and n are defined as in claim 2, and Col is a dye, a dye precursor or a moiety containing a series of conjugated π bonds.

5. A photographic recording material according to claim 4 characterized in that J is -(CR₃R⁴)_m-, -NR⁵-, -NRS-S02-, -NR⁵-PO₂-, -NR⁵-PO₃-, -NR³CO-, -NR³COR⁵-, -O-, OR⁵-, -SR⁵,

-PO₂R⁵- or -PO₃R⁵-, and R³ and R⁴ each independently represents hydrogen, or a substituted or unsubstituted alkyl, aryl, aralkyl or alkaryl group; R⁵ is a substituted or unsubstituted alkyl, aryl, aralkyl or alkaryl group; and m is an integer of from 1 to 16.

6. A photographic recording material according to claim 4 characterized in that G is OH; Y represents the atoms necessary to complete a naphthalene nucleus; Col is a dye; J is -NHCOR⁵- or -OR⁵-; and R⁵ is a substituted or unsubstituted alkyl, aryl, aralkyl or alkaryl group and n is 2.

7. A photographic recording material according to claim 4 characterized in that said dye image-providing material is a redox dye-releasing compound and said deactivating compound is present at a concentration of from 5 to 25 mg/m² of element.

8. A photographic recording material according to any of claims 1 to 7 which also comprises an alkaline processing composition comprising carbon black and means containing same for discharge within said recording material and a transparent cover sheet characterized in that said deactivating compound is present in at least one of said opaque layer or processing composition.